CN101428847B - Process for producing nanostructured tin dioxide lithium ion battery negative pole material - Google Patents

Process for producing nanostructured tin dioxide lithium ion battery negative pole material Download PDF

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CN101428847B
CN101428847B CN2008100515939A CN200810051593A CN101428847B CN 101428847 B CN101428847 B CN 101428847B CN 2008100515939 A CN2008100515939 A CN 2008100515939A CN 200810051593 A CN200810051593 A CN 200810051593A CN 101428847 B CN101428847 B CN 101428847B
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lithium ion
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battery negative
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CN101428847A (en
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陈接胜
张锋
李国栋
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Jilin University
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Abstract

The invention belongs to the preparation field of the anode material of a lithium ion battery, and in particular relates to a method for preparing metal oxide electrode material with a nanometer structure by utilizing the in-situ synthesis method. The internal structure and the dimension of a hollow micro-sphere obtained are controlled through adjusting the pH value of a system by utilizing hydrochloric acid. Raw materials in the invention are common and are easy to obtain; an organic solvent is not required during the preparation process; the preparation process is simple; the synthesis of template materials and the participation of a surface active agent are not required during the synthetic process; the requirements to the device are low, the time consumption is less and the preparationprocess is simple; and a main by-product during the preparation process is water and carbon dioxide and is environment-friendly. The raw materials used in the invention are common; and the preparation conditions are not restricted by areas. The hollow tin dioxide micro-spheres have higher application prospect in the filed of electrode material, catalyst carriers and the like. The method has the advantages of cheap and easily obtained raw materials, simple preparation process, and unrestricted preparation conditions by areas, and is suitable for massive industrial production.

Description

The preparation method of nanostructured tin dioxide lithium ion battery negative pole material
Technical field
The invention belongs to the lithium ion battery negative material preparation field, be specifically related to a kind of preparation method who utilizes in-situ synthesis to prepare metal oxide cell negative electrode material with nanostructure.
Background technology
Because the limited reserves and the problem of environmental pollution of world's fossil energy are more and more serious, people begin to develop novel, that reserves are abundant and cheap energy gradually.Lithium ion battery it is had a wide range of applications in modern society, and development trend is become better and better because it has higher output voltage, bigger cell container, long work-ing life and advantage such as use temperature more widely.But it is, also more and more higher to the requirement of the capacity of lithium ion battery along with the continuous development of society.The amount of capacity of lithium ion battery depends primarily on the capacity of the positive and negative pole material of battery.At present, the negative material that is extensive use of lithium ion battery in the society mainly is a graphitized carbon material, because the theoretical capacity of graphitized carbon material has only 372mA h g -1So more and more can not satisfy the demand of social development as the lithium ion battery of negative material with graphitized carbon material, so people begin to seek the novel negative material of alternative conventional graphite carbon material and improve the use capacity of lithium ion battery, thereby satisfy the demand of social development.
In the past few years, multiple material is developed, and has studied their performances as lithium ion battery negative material, and wherein the research of a variety of materials has obtained breakthrough progress.Up to the present, these negative materials newly developed mainly include low graphitized carbon material (amorphous carbon material and gac), metal oxide, metallic sulfide and metal alloy etc.Though these novel negative materials all have the incomparable advantage of a lot of graphitized carbon materials, equally also there are some shortcomings in they, and these shortcomings have seriously hindered the practical application of these novel negative materials.Low graphitized carbon material generally is made up of graphite microcrystal and amorphous domain.As negative material the time, storage lithium mechanism is no longer as single intercalation mechanism in the graphitized carbon material storage lithium process, but the coexistence of multiple mechanism, as lithium dimer storage lithium mechanism, multilayer lithium storage storage lithium mechanism, individual layer ink sheet molecule storage lithium mechanism and micropore storage lithium mechanism etc.Low graphitized carbon material generally all has the reversible capacity that is higher than graphitized carbon material far away as lithium ion battery negative material the time, but their cycle performance is all undesirable, reversible capacity generally along with decaying of charge and discharge cycles very fast.This shortcoming has seriously hindered the practical application of low graphitized carbon material aspect lithium ion battery negative material.Along with electrode materials research development constantly, people begin sight is transferred to metal (alloy), metal oxide and metallic sulfide, discover that most of metals (alloy), metal oxide and metallic sulfide can store up lithium by reversible, and capacity is far longer than the capacity of graphite.In numerous metals, the most noticeable with metallic tin, tin-based alloy, tin-based oxide and tinbase sulfide.Metal or alloy are as negative material the time, though very high lithium storage content can be provided, but metal or alloy exist bigger volume change in charge and discharge process, so increase along with cycle index, these electrode materialss can be chipping, and then make the battery electrode inactivation, also exist the danger that causes internal short-circuit of battery and produce blast simultaneously.There are the big shortcoming of volume change equally in tin-based oxide or sulfide in as the process of ion cathode material lithium.These shortcomings have seriously hindered tin-based oxide or the application of sulfide aspect lithium ion battery negative material.Along with further developing of research, it is found that the tin-based oxide with special construction can improve the chemical property of metal oxide to a great extent.Present modal method is exactly the size that changes oxide particle, oxide particle with nano-scale has bigger specific surface area, there is bigger space between the particle, this makes oxide particle can reduce the influence of volume change in charge and discharge process, thereby make electrode be not easy fragmentation, prolong battery work-ing life and improve safety performance.And nearest result of study shows that the tin-based oxide with hollow structure not only can reduce the influence that the oxide compound volume changes in the charge and discharge process, but also can increase lithium storage content.The synthetic method of the tin-based oxide of hollow structure mainly contains solvent-thermal method, template etc. at present, but all there are some shortcomings in these methods.The oxide structure of solvent-thermal method preparation is unpredictable, needs some organic solvents in addition, and waste liquid produces environment and pollutes.Template building-up process complexity, the building-up process of mould material trouble needs the oversize time, and product yield is lower and need be exactly to remove oxide structure is destroyed in addition by template.
At present, also do not have effective means can control the internal structure and the size of tindioxide hollow micron ball effectively, therefore, the method for seeking the hollow tindioxide microballoon of controlledly synthesis effectively has very big effect to the development of tin base cathode material.
Summary of the invention
The problem to be solved in the present invention is the deficiency at preparation method in the technical background, the synthetic and air calcination method by simple hydro-thermal, and original position synthesizes the tindioxide SnO with nucleocapsid structure or hollow structure 2, i.e. the SnO of nanostructure 2Lithium ion battery negative material.Nucleocapsid structure SnO 2Inner solid core size controlled (0.0～1.5 μ m), hollow ball-type SnO 2Size also can control (0.3～2.0 μ m).
The present invention utilizes common Resorcinol, formaldehyde, hydrochloric acid and tin protochloride to be raw material, prepare spherical stannous compound/resol complex body by hydro-thermal synthetic method, utilize the resol in the air calcination removal complex body, simultaneously stannous compound is oxidized to tindioxide, the tindioxide of gained has kept the globosity of mixture.Consumption that utilize to regulate hydrochloric acid is controlled the hydrolysis of stannous ion, and then control stannous compound shared ratio in complex body, thereby obtains the tiny balloon of different internal structure.The present invention is of very high actual application value.
The SnO of original position synthetic nanostructure of the present invention 2The preparation method of lithium ion battery negative material, its step is as follows:
(1) with 1.00～3.00g SnCl 22H 2O and 1.0～4.0g Resorcinol are dissolved in 10～40ml deionized water, and magnetic agitation is even;
(2) in above-mentioned system, add the hydrochloric acid that 0.0～8.0mL concentration is 20～37wt%, after stirring, add 2.0～10.0mL, 20～40wt% formaldehyde solution fast, vigorous stirring 10～40 seconds, then mixing solutions is transferred in the teflon-lined stainless steel cauldron of 35～60mL, in 65～90 ℃ baking oven, react 24～96h then, naturally cool to room temperature, obtain red intermediate product Sn (OH) Cl/ resol;
(3) intermediate product that will go up step utilize the deionized water suction filtration, wash to the pH value be 5～7, dry down at 40～100 ℃ then;
(4) product that will go up step places tube furnace, and in air, 450～650 ℃ of calcining 1～5h down obtain the white solid product, i.e. the SnO of nanostructure 2Lithium ion battery negative material.
Further, in the aforesaid method, be with 2.00～2.25g SnCl 22H 2O and 1.6～3.2g Resorcinol are dissolved in 25～35ml deionized water;
Further, in the aforesaid method, be in above-mentioned system, add 0.0～5.0mL, concentration is the hydrochloric acid of 30～37wt%, after stirring, add 3.5～7.0mL, 37～40wt% formaldehyde solution fast, vigorous stirring 20～30 seconds, then mixing solutions is transferred in the teflon-lined stainless steel cauldron of 45～60mL, in 70～85 ℃ baking oven, react 40～48h then, naturally cool to room temperature, obtain red intermediate product Sn (OH) Cl/ resol;
Further, in the aforesaid method, be with intermediate product utilize the deionized water suction filtration, wash to the pH value be 6～7, down dry at 50～80 ℃ then;
Further, in the aforesaid method, be that the product with last step places tube furnace, in air, 500～550 ℃ of calcining 3～4h down obtain the white solid product, i.e. the SnO of nanostructure of the present invention 2Lithium ion battery negative material.
The present invention utilizes common Resorcinol, formaldehyde, hydrochloric acid and tin protochloride to be raw material, the tindioxide microballoon that the calcining preparation has hollow structure in the synthetic and air by hydro-thermal.The microballoon of this method preparation can be a hollow structure completely, it also can be nucleocapsid structure with solid core, microballoon is to be piled up by tin dioxide nano-particle to form, and the size of the size of microballoon, solid core can be controlled by the consumption of regulating hydrochloric acid.Raw material in this inventive method is common to be easy to get, in the process of preparation, do not need organic solvent, preparation process is simple, the method for preparing tiny balloon with most of template is very different, the present invention does not need the earlier synthetic mould material of substep, does not need the participation of tensio-active agent in the synthesizing inorganic thing process, can be by changing the structure and the size of simple experiment condition control product, the products therefrom structural integrity, big or small homogeneous.
Among the present invention the tindioxide microballoon the preparation method low for equipment requirements, consuming time few, preparation process is simple, the main by product in the preparation process is water and carbonic acid gas, and is environmentally friendly.Raw materials used common in the invention, preparation condition is not subjected to territorial restrictions.
The present invention is particularly suitable for industrial mass production, has very important significance to the exploitation of hollow structure tindioxide microballoon is synthetic.Being directed to does not especially currently have simple method can control synthetic hollow tindioxide microballoon effectively, and the present invention can synthesize the various hollow tindioxide microballoon with different internal structure and size simply.The various tindioxide microballoons that the present invention obtains are in support of the catalyst, and fields such as air-sensitive and humidity-sensitive material and electrode materials all can have broad application prospects.
Description of drawings
Fig. 1: the XRD figure of the hollow tindioxide microballoon for preparing under the different hydrochloric acid consumption conditions;
The stereoscan photograph (a) and the transmission electron microscope photo (b) of the tindioxide microballoon of Fig. 2: embodiment 1 preparation;
The stereoscan photograph (a) and the transmission electron microscope photo (b) of the tindioxide microballoon of Fig. 3: embodiment 2 preparations;
The stereoscan photograph (a) and the transmission electron microscope photo (b) of the tindioxide microballoon of Fig. 4: embodiment 3 preparations;
The stereoscan photograph (a) and the transmission electron microscope photo (b) of the tindioxide microballoon of Fig. 5: embodiment 4 preparations;
The stereoscan photograph (a) and the transmission electron microscope photo (b) of the tindioxide microballoon of Fig. 6: embodiment 6 preparations;
The stereoscan photograph (a) and the transmission electron microscope photo (b) of the tindioxide microballoon of Fig. 7: embodiment 7 preparations;
The charge and discharge cycles curve of the tindioxide of Fig. 8: embodiment 2 and embodiment 3 preparations, current density 100mA/g.
Fig. 1 is the XRD figure of the tindioxide microballoon for preparing under the different hydrochloric acid consumption conditions, among the figure each diffraction peak all with rutile-type SnO 2Characteristic peak match, illustrate that product is the SnO of pure phase 2, the diffraction peak explanation microballoon of broad is assembled by nanoparticle, and (k is 0.89 for the Scherrer constant by Scherrer equation d=K λ/(β cos θ); λ is X ray wavelength (nm); θ is a diffraction angle; β is a diffraction peak halfwidth degree) calculate and learn that the nanoparticle size that constitutes the tindioxide microballoon is between 10～20nm.
Fig. 2 is stereoscan photograph and the transmission electron microscope photo that does not add the tindioxide microballoon of hydrochloric acid preparation, can see clearly that in photo the tindioxide microballoon has tangible nucleocapsid structure, wherein the whole size of tindioxide microballoon is 2 μ m, the diameter of solid core is 1.5 μ m, and outer casing thickness is 250nm.
Fig. 3 is for adding the stereoscan photograph and the transmission electron microscope photo of tindioxide microballoon that 0.5 ml concn is the hydrochloric acid preparation of 37wt%, can see that in photo the tindioxide microballoon that obtains remains nucleocapsid structure, the microballoon size is 2 μ m, the solid core size is 0.8 μ m, and outer casing thickness is approximately 200nm.
Fig. 4 is for adding the stereoscan photograph and the transmission electron microscope photo of tindioxide microballoon that 1.0 ml concns are the hydrochloric acid preparation of 37wt%, can find out clearly from photo, the tindioxide microballoon is hollow fully, the about 2 μ m of microballoon size, and wall thickness is greatly about 100nm.
Fig. 5 is for adding the stereoscan photograph and the transmission electron microscope photo of tindioxide microballoon that 1.5 ml concns are the hydrochloric acid preparation of 37wt%, the hollow tindioxide microballoon size that can see gained about 1.5 μ m, the about 80nm of wall thickness.
Fig. 6 can see that the hollow tindioxide ball size of gained is about 500nm, the about 50nm of wall thickness for adding the stereoscan photograph and the transmission electron microscope photo of tindioxide microballoon that 4.5 ml concns are the hydrochloric acid preparation of 37wt%.
Fig. 7 can see that the hollow tindioxide ball size of gained is about 300nm, the about 50nm of wall thickness for adding the stereoscan photograph and the transmission electron microscope photo of tindioxide microballoon that 5.0 ml concns are the hydrochloric acid preparation of 37wt%.
Fig. 8 is the charge-discharge performance of nucleocapsid structure and hollow structure tindioxide, also has very big reversible capacity even can see two kinds of structures after through 15 circulations, in first time charge and discharge cycles, and the SnO of nucleocapsid structure 2Have charging capacity (lithium ion embedding) 2359mAh/g and loading capacity (lithium ion is deviate from) capacity 1171mAh/g, coulombic efficiency is 49.6%.The SnO of hollow structure 2Have charging capacity 1729mAh/g and loading capacity capacity 908mAh/g, coulombic efficiency is 52.5%.Irreversible capacity in the charge and discharge cycles mainly is because reduction SnO for the first time 2Form Li 2O causes.But in second time charge and discharge cycles, cycle performance just is much improved.The SnO of nucleocapsid structure 2Have charging capacity 1316mAh/g and loading capacity capacity 1122mAh/g, coulombic efficiency is 85.3%.The SnO of hollow structure 2Have charging capacity 990mAh/g and loading capacity capacity 872mAh/g, coulombic efficiency is 88.1%.Even through after 15 charge and discharge cycles, the SnO of nucleocapsid structure 2Still have charging capacity 815mAh/g and loading capacity capacity 732mAh/g, coulombic efficiency is 90.0%.The SnO of hollow structure 2Have charging capacity 600mAh/g and loading capacity capacity 540mAh/g, coulombic efficiency is 90%.
Embodiment
Embodiment 1:
With 2.25g SnCl 22H 2O and 3.2g Resorcinol are dissolved in the 30ml deionized water, stir, in 5 seconds, add 7.0mL 36wt% formaldehyde solution then, vigorous stirring 25 seconds, mixing solutions is transferred in the teflon-lined stainless steel cauldron of 45mL, in 85 ℃ baking oven, reacted 48h then, naturally cool to room temperature, with the intermediate product suction filtration that obtains, wash to the pH value be 7, dry down at 80 ℃ then.At last intermediate product is placed tube furnace, in air, calcine 4h down for 550 ℃, obtain the tindioxide microballoon of nucleocapsid structure, the microballoon size is approximately 2 μ m, and the solid core size is 1.5 μ m.
Embodiment 2:
Experimental technique just adds the hydrochloric acid that 0.5mL concentration is 37wt% with embodiment 1, obtains the tindioxide microballoon of nucleocapsid structure equally, and the microballoon size is approximately 2 μ m, and the solid core size is 0.8 μ m.
Embodiment 3:
Experimental technique just adds the hydrochloric acid that 1.0mL concentration is 37wt% with embodiment 1, obtains the tindioxide microballoon of hollow structure, and the microballoon size is approximately 2 μ m.
Embodiment 4:
Experimental technique just adds the hydrochloric acid that 1.5mL concentration is 37wt% with embodiment 1, obtains the tindioxide microballoon of hollow structure, and the microballoon size is approximately 1.5 μ m.
Embodiment 5:
Experimental technique just adds the hydrochloric acid that 2.0mL concentration is 37wt% with embodiment 1, obtains the tindioxide microballoon of hollow structure, and the microballoon size is approximately 0.8 μ m.
Embodiment 6:
Experimental technique just adds the hydrochloric acid that 4.5mL concentration is 37wt% with embodiment 1, obtains the tindioxide microballoon of hollow structure, and the microballoon size is approximately 500nm.
Embodiment 7:
Experimental technique just adds the hydrochloric acid that 5.0mL concentration is 37wt% with embodiment 1, obtains the tindioxide microballoon of hollow structure, and the microballoon size is approximately 300nm.
Embodiment 8:
Experimental technique is with embodiment 1, just with SnCl 22H 2The quality of O and Resorcinol becomes 1.6g and 3.5g, obtains the tindioxide microballoon of nucleocapsid structure, and the microballoon size is approximately 2 μ m, and the solid core size is 1.2 μ m.
Embodiment 9:
Experimental technique just adds the hydrochloric acid that 0.5mL concentration is 37wt% with embodiment 8, obtains the tindioxide microballoon of nucleocapsid structure equally, and the microballoon size is approximately 1.5 μ m, and the solid core size is 0.8 μ m.
Embodiment 10:
Experimental technique just adds the hydrochloric acid that 2.0mL concentration is 37wt% with embodiment 8, obtains the tindioxide microballoon of hollow structure, and the microballoon size is approximately 0.8 μ m.
Embodiment 11:
Experimental technique just adds the hydrochloric acid that 3.0mL concentration is 37wt% with embodiment 8, obtains the tindioxide microballoon of hollow structure, and the microballoon size is approximately 0.6 μ m.
Embodiment 12:
Experimental technique just adds the hydrochloric acid that 4.0mL concentration is 37wt% with embodiment 8, obtains the tindioxide microballoon of hollow structure, and the microballoon size is approximately 500nm.
Embodiment 13:
The product of embodiment 2 and embodiment 3 is prepared as follows into simulation electrode: tindioxide, acetylene black and polyvinylidene difluoride (PVDF) (PVDF) mix according to mass ratio at 8: 1: 1, adding the N-Methyl pyrrolidone solvent sizes mixing, be coated on the Copper Foil that thickness is 20 μ m 100 ℃ of following vacuum-drying 24h then equably.Simulated battery is assembled in the glove box that is full of purity 99.999% argon gas.Carry out charge-discharge test under the condition of current density 100mA/g, the result as shown in Figure 8.

Claims (5)

1. the SnO of nanostructure 2The preparation method of lithium ion battery negative material, its step is as follows:
(1) with 1.00～3.00g SnCl 22H 2O and 1.0～4.0g Resorcinol are dissolved in 10～40ml deionized water, and magnetic agitation is even;
(2) in above-mentioned system, add the hydrochloric acid that 0.0～8.0mL concentration is 20～37wt%, after stirring, add 2.0～10.0mL, 20～40wt% formaldehyde solution fast, vigorous stirring 10～40 seconds, then mixing solutions is transferred in the teflon-lined stainless steel cauldron of 35～60mL, in 65～90 ℃ baking oven, react 24～96h then, naturally cool to room temperature, obtain red intermediate product Sn (OH) Cl/ resol;
(3) intermediate product that will go up step utilize the deionized water suction filtration, wash to the pH value be 5～7, dry down at 40～100 ℃ then;
(4) product that will go up step places tube furnace, and in air, 450～650 ℃ of calcining 1～5h down obtain the white solid product, i.e. the SnO of nanostructure 2Lithium ion battery negative material.
2. the SnO of nanostructure as claimed in claim 1 2The preparation method of lithium ion battery negative material is characterized in that: be with 2.00～2.25g SnCl in the step (1) 22H 2O and 1.6～3.2g Resorcinol are dissolved in 25～35ml deionized water.
3. the SnO of nanostructure as claimed in claim 1 2The preparation method of lithium ion battery negative material, it is characterized in that: be that adding 0.0～5.0mL, concentration are the hydrochloric acid of 30～37wt% in the step (2), after stirring, add 3.5～7.0mL, 37～40wt% formaldehyde solution fast, vigorous stirring 20～30 seconds, then mixing solutions is transferred in the teflon-lined stainless steel cauldron of 45～60mL, in 70～85 ℃ baking oven, react 40～48h then, naturally cool to room temperature, obtain red intermediate product Sn (OH) Cl/ resol.
4. the SnO of nanostructure as claimed in claim 1 2The preparation method of lithium ion battery negative material is characterized in that: in the step (3) be with intermediate product utilize the deionized water suction filtration, wash to the pH value be 6～7, down dry at 50～80 ℃ then.
5. the SnO of nanostructure as claimed in claim 1 2The preparation method of lithium ion battery negative material is characterized in that: step is that product is placed tube furnace in (4), in air, calcines 3～4h down, obtains the white solid product, i.e. the SnO of nanostructure for 500～550 ℃ 2Lithium ion battery negative material.
CN2008100515939A 2008-12-15 2008-12-15 Process for producing nanostructured tin dioxide lithium ion battery negative pole material Expired - Fee Related CN101428847B (en)

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